Green substantive dyes of the anthraquinone series



United StatesPatentO M 2,779,772 GREEN SUBSTANTIVE DYES OF THE ANTHRAQUINONE SERIES Wolfgang Frey, Neue Welt, near Basel, Switzerland, assignor, by mesne assignments, to, Saul & C05, asnominee of Fidelity Union Trust Company 7 No Drawing. Application October 5, 1952,

Serial No. 313,350 y k Claims priority, application Switzerland October 18, 1951 6 Claims. (Cl. 260-368), a

The present invention relates to green substantive dyes of the anthraquinone series.

Copending application, Ser. No. 202,418, filed December 22, 1950 (and which has since matured as U. S.

Patent No. 2,623,884), discloses green substantive dyestuffs prepared by condensing one mol of a compound of the formula NH: ll 1 I i a o NHR (1) wherein R stands for a phenyl or diphenyl radical containing 21 free amino group and which may be further substituted, with another mol of a similarly or difierently substituted starting compound of the same general formula, through the medium of a maleic or fumaric acid derivative. In case two different starting compounds are employed, they are used in substantially molecular proportions. The thus-obtained dyestuffs are of very good iastness to light. The wet-fastness properties of some of these dyestuffs are capable of improvement. Those dyestuffs characterized by outstanding fastness properties are not always of sufiicient solubility for certain applications, particularly for apparatus dyeing.

A primary object of the present invention is the embodiment of a group of dyestuifs which, while possessing the advantages of the aforesaid dyestufis, are free of the enumerated shortcomings.

This object is realized, according to the present invention, which provides a group of substantive dyestuifs of the anthraquinone series which combine very good light fastness properties with good wet-fastness properties, good solubility and good exhaustion capacity. These improved dyestuffs are obtained, according to the invention, by condensing a 1-aminoanthraquinone-Z-sulfonic acid of the formula i i NH-R (2 wherein R stands for a phenyl or diphenyl radical which contains a free amino groups and which may be further substituted by alkyl, alkoxy or SOaH, x stands for hydro gen, SOsH or halogen, and y stands for hydrogen or halogen, in non-molecular proportion with at least one different l-amino-anthraquinone-Z-sulfonic acid of Formula 2 and/or at least one yellow aminoazo dyestufi, through the medium of a dicarboxylic acid halide of the formula 2OGC=(|J-CO-z wherein z stands for chlorine or bromine, and A stands for hydrogen, methyl, chlorineor'bromine, one mol of r 2,779,772 Patented an. 2?,

0) a o N112 II f SO;M

( NHR 7 wherein R stands for a phenyl or diphenyl radical which contains a free amino group and which may be substituted by lower alkyl such as methyl, ethyl and the like, by lower alkoxy such as methoxy, ethoxy and the like, or by SOaH, and M stands for H, Li, Na or K, and nucleus I may carry in the positions 5, 6, 7 or 8 a sulfonic acid group or in the positions 6 or 7 a halogen atom, e. g. chlorine or bromine, or in the positions 6 and 7 two chlorine atoms. a

The starting compounds of Formula i are obtained by the condensation of a 1-amino-4-halogenanthraquinone-2- sulfonic acid which corresponds to the type formula i) Halogen wherein nucleus I may be substituted as hereinbefore set forth, with p-phenylenediamine or benzidine, or with a pphenylenediamine or a benzid ine, wherein the phenyl nuclei are substituted by lower alkyl, lower alkoXy or SOsI-I, as previously indicated in connection with the definition of R. Starting compounds of Formula i thus comprise, for example, the condensation products of lamino-4-bromo-anthraquinone-Z-sulfoni acid with 1,4-diamino-benzene, l,4-diamino-2-1nethylbenzene, 1,4-diamino-Z-methoxybenzene, l,4-diaminobenzene-Z-sulfonic acid and 4,4-diaminodiphenyl3-sulf0nic acid; the condensation products of 1-amino-4-bromo-anthraquinone- 2,5, -2,6-, -2,7- and -2,8-disulfonic acid as well as mixtures of these sulfonic acids with p-phenylenediamine, benzidine, 4,4-diaminodiphenyl-3sulfonic acid, 4,4'-diamino-3,3'-dimethyldiphenyl and 4,4 diamino 3,3 dimethoxydiphenyl; the condensation products of 1-amino-4-bromo-6- and -7-chloro-anthraquinone-Z-sulfdnic acid with 4,4-di amincdiphenyl-3-sulfonic acid; the condensation product of 1-amino-4-bromo-6,7-dichloro-ahthraquinone 2 sulfonic acid with 4,4-diaminodiphenyl-3-sulfonic acid; etc. Especially interesting is the simplest compound which corresponds to the formula SOsH because, for example when condensed with fumaricacid dichloride, it yields a green dyestutf of outstanding fast mess to light and good wash-fastness properties, although its solubility in the dyebath is not entirely satisfactory. However, the solubility of the dyestufi can be improved according to the invention so that it can be employed in apparatus dyeing when, in the preparation thereof, other starting compounds of similar structure or yellow aminoazo dyestuffs are added in non-molecular proportions, i. e.

compound of the formula O N112 ll l l l Nit-Orrin and 1 mol of the compound of the formula HOsS with 4 mols of furnaric acid dichloride yields a dyestufi capable of use in apparatus dyeing and having good Wash fastness and good exhaustion capacity, while the mixture of:

2 mols (4)fumaryl(4) 1 mol 4 fumaryl( 5) 1 mol 4 fumaryl( 6) gives rise to difficulties in apparatus dyeing. A comparative solubility test may be carried out as follows: 20 cc. of a solution of 0.1 gram of dyestutf in 280 cc. of distilled Water, to which 20 cc. of an aqueous sodium sulfate solution'of 10% strength have been added, are heated to 60 C. and filtered through a filter paper of cm. diameter, folded into the shape of a cone. In the first case, the solution passes without residue through the filter; in the second case, substantially all the dyestuff remains on the filter asa blackish green deposit, while the filtrate runs through in a pale gree'njcolor.

The number of components is unlimited. Satisfactory dyestuffs can be prepared as well with 2 components, provided they do not stand in the mol proportion 1:1, as with 3,4 or more components. The desired improvement of the'dyestiiffs is obtained, when'the portion of the starting materials which are added in small amounts, corresponds to at least 10 percent of the molecules of the mixture. If there are two'components, the deviation of the 1:1 proportionhas to beat least of about 10 percent. This is not to say that all mixtures yield dyestuffs ofequally good solubility -and'goodexhaustion capacity. The examples, hereinafter set forth, illustrate proportions which produce satisfactory results.

'As' components, in addition to the anthraquinone derivatives, use can also be made of yellow aminoazo dyestulfs, such for example as 4-a'i'r'1inoazobenzene-4'-sulfonic acid, 4-(4"-amino)-benzoylaminoazobenzene-3',4-disulfonic acid, and yellow aminoazo compounds of the naphthalene, stilbene and pyrazolone series, aminodisazo dyestuffs, etc. They improvesolubility characteristics and simultaneously displace the shade in a valuable direction toward the yellow-green.

. The employed dihalides of maleic and fumaric acids are the chlorides and bromides of fumaric acid, of chloroand bromo-fumarie acid and of mesaconic acid, and their stereoisomer'ic forms. The dicarboxylic'acid halides substitutd at the -=C=*C bridge yield, in comparison with those'which are not so substituted, dye shades which are terials, the formation of undesired bluish dyestufis can be avoided.

The dyestuffs of the invention are prepared by dissolving the mixture of starting materials in water and adding the calculated amount of acid chloride, if necessary with a slight exces's, at substantially normal temperature (about 030 C.) and while maintaining a substantially neutral reaction by the addition of acid-binding agents. The formed dyestuffs are isolated by salting out or by precipitating out by the addition of acid, etc. In dry form, they are dark green to greenish black powders which dissolve with bluish green, green to yellowish green coloration in water. From these solutions, the dyes draw onto fibers and articles of natural or regenerated cellulose in cor responding shades, and yield dyeings of outstanding fastness to light and good fastness to washing.

The following examples illustrate the invention without, however, being restrictive thereof. In the examples, the parts, unless otherwise indicated, are parts by weight. The employed intermediates of the anthraquinone series are summarized in the following table; they are identified in the examples by the corresponding Roman numerals.

O NHz r I l so3n NHR

N R x 1/ Position of- I --NH:

OCH:

1r -C NH SO3H s 111 Nrn -SO3H 7 IV -NH2 -o1 -01 0 7 v -NH2 SO3H (5 vr NH2 SOaH 4 VIII OONHB son-r IX NH, SO3H 7 CH; CH;

x1 maria SO3H s xrr ---NH2 --o1 7 sour x111 NH2 Br s Example 1 4.7 parts of Compound VII, 1.65 parts of Compound V, 1.7 parts of Compound IX and 1.65 parts of Compound VIII are dissolved in 400 parts of water with addition of 1.2 parts of lithium carbonate. At -3 and while stirring thoroughly, 10.5 parts by volume of a molar solution of fumaryl chloride in carbon tetrachloride are added. By the slow dropwise addition of 10 parts by volume of an aqueous sodium hydroxide solution of 10% strength,.the reaction is maintained at a pH of 4.5 to 6.5. Upon completion of the condensation, the carbon tetrachloride is distilled oil, the reaction mixture adjusted to alkalinity with aqueous sodium hydroxide solution, and the formed dyestuff filtered off at 20. It is washed with aqueous sodium chloride solution and dried.

The dyestuit is a dark-green powder which dissolves with green coloration in water, and dyes cotton and regenerated cellulose in green shades of very good light fastness and wet-fastness.

A similar dyestufi is obtained when, while otherwise proceeding as aforedescribed in this example, the fumaryl dichloride is replaced by an equivalent quantity of maleinyl dichloride or of fumaryl dibromide.

Example 2 5 parts by volume of an aqueoussodium hydroxide solution of strength, 4.1 parts (1.0 molecular proportion) of Compound VII, 2.2 parts (0.5 molecular proportion) of Compound I, 1.25 parts (0.25 molecular proportion) of Compound II and 1.45 parts (0.25 mole cular proportion) of Compound V are stirred into 400 parts of water. When dissolution is complete, the solution is cooled to approximately 0, and 10.5 parts .by volume of a molar solution of fumaryl dichloride in carbon tetrachloride are added. The reaction mixture .is kept weakly acid with dilute aqueous sodium hydroxide solution. Upon completion of the condensation, the carbon tetrachloride is distilled ofi, the reaction mass adjusted to strong alkalinity with aqueous sodium hydroxide solution, and the formed dyestufi then filtered off at 20. The filtrate is washed with an aqueous sodium sulfate solution of 7% strength and then dried.

The dyestufl dissolves with green coloration in water and dyes cotton and regenerated cellulose a fast green.

If while proceeding as aforedescribed in the present example, the fumaryl'dichloride is replaced by an equivalent mixture of fumaryl dichloride and mesaconyl dichloride--the latter for example in an amount of 0.5 part--then a bluish green dyestufi' of similar properties is obtained.

Example 3 5.9 parts (1L4 molecular proportions) of Compound VII, i. e. of the compound of the. formula 0 IITH:

i and 1.4 parts (0.3 molecular'proportion)"of Compound VI, i. e. of the compound of the formula 0 NH: H 1

0 NH- NHz SOsH and 0.85 part, i. e. 0.3 molecular proportion, of 4-amino- 1,l'-azobenzene-4-sulfonic acid are dissolved in 400 parts of water, with addition of 0.7 part of lithium carbonate. At 05 10.5 parts by volume of a molar fumaryl dichloride solution in carbon tetrachloride and 8 parts by volume of an aqueous sodium hydroxide solution of 10% strength are simultaneously added dropwise in such manner that the pH of the re action mixture remains between 4.5 and 6. Upon completion of the condensation, the reaction mixture is acidified, the separated dyestufi is suction-filtered oil, the weakly acid filter cake triturated with the amount of sodium carbonate necessary for neutralization and then dried.

The thus-obtained dyestufi dyes cotton and regenerated cellulose, from aqueous solution, in a pretty green shade of good fastness properties.

By omitting the 0.85 part (0.3 molecular proportion) 'of 4-amino-l,1'-azobenzene-4-sulfonic acid and using in its stead 1.4 parts (0.3 molecular proportion) of Compound VI, i. e. of the compound of formula 0 NHz II son-r ll 0 NH Nrn 1.45 parts (0.22 molecular proportion) of Compound IV, 2.2 parts (0.45 molecular proportion) of Compound II and 5.45 parts (1.33 molecular proportion) of Compound VII are dissolved in 350 parts of water, with the aid of 0.6 part of lithium carbonate. At 3, 1.6 parts of fumaryldichloride are added and, while agitating thoroughly, the temperature is allowed to rise to 20. During this period, the mixture is maintained neutral by the additionof about 9 parts by volume of aqueous sodium hydroxide solution of 10% strength. The resultant dyestufi is worked up asin the preceding examples; it is a dark powder which dissolves with green coloration in water and dyes cotton and regenerated cellulose in Example 5 U 3.8 partsofCompoundV, 4.2 parts of Compound III and 1.9 parts of 4'-amino-1,l-azobenzene-4-sulfonic acid 3 are dissolved in 400 parts of an aqueous solution of lithium carbonate of 0.15% strength. The reaction mix- 6' ture is cooled to -15", and 1.1 parts by volume of fumaryl dichloride are added. The reaction mixture is maintained weakly acid by the dropwise addition of an aqueous sodium hydroxide solution of 10% strength.

When the dichloride is used up, the reaction mixture is Example 6 1.45 parts (0.25 molecular proportion) of Compound V, i. e. of the compound of the formula r ii n utj N1-n and 1.25 parts (0.25 molecular proportion) of Compound II, i. e. of the compound of the formula SOsH and 6.15 parts (1.5 molecular proportions) of Compound VII, i. e. of the compound of the formula and 1 part of lithium carbonate are dissolved in 350 parts of water. added, and the reaction mixture agitated thoroughly while being maintained quite weakly acid by means of dilute aqueous sodium hydroxide solution. Upon completion of the condensation, the reaction mixture is adjusted to strong alkalinity with the aid of aqueous sodium hydroxide solution of 29% strength, and the formed dyestuii suction-filtered oil and washed with aqueous sodium chloride solution.

The thus-obtained dyestuii is easily soluble in the dyebath and dyes cotton and regenerated cellulose in green shades with good exhaustion. The dyeings are outstandingly light-fast and wet-fast.

A similar dyestufr" is obtained when, while otherwise proceeding as described in the present example, the 1.45 parts of Compound V are replaced by 1.45 parts of a technical mixture of Compounds X and XI.

Example 7 It dissolves in waterwith bluish-green coloration and At 5, 1.6 parts of fumaryl dichloride are dyes cottonand regenerated cellulose in bluish-green slrades'of excellent properties.

9 Example 8 5.9 parts (1.45 molecular proportions) of Compound VII and 2.8 parts (0.55 molecular proportion) of Compound II are dissolved, together with 0.7 part of lithium carbonate, in 300 parts of water, and the reaction mixture cooled to 0+5". Then, Within a period of /2 hour and while stirring, 1.0.5 parts by volume of a molar solution of fumaryl dichloride in carbon tetrachloride are added, the reaction mixture being maintained weakly acid by the addition of aqueous caustic soda solution of 10% strength. Upon completion of the reaction, the carbon tetrachloride is distilled off. After strong acidifica'tion, the formed dyestufi acid is suction-filtered off hot; by pasting with sodium carbonate it is rendered neutral, after which it is dried.

' The dyestufl thus obtained is a dark green powder which draws well from aqueous solution onto cotton and regenerated cellulose, and remains dissolved in the dyebath even after the addition of salt. Its dyeings, which are green, are outstandingly light-fast and wet-fast.

Example 9 Into 350 parts of water, there are stirred 0.6 part of lithium carbonate, 5.45 parts of Compound VII, 1.1 parts of Compound II and 1.9 parts of 4-(4"-aminobenzoyl)-amino-1,1'-azobenzene 3,4 disulfonic acid. When dissolution is complete, 5.8 parts by volumeof a two-molar solution of furnaryl dichloride in trichlorethylene are added at 040, and the reaction mixture maintained at pH 5*6 with approximately 7 parts of aqueous sodium hydroxide solution of 10% strength. The trichlorethylene is subsequently distilled off, the dyestuff precipitated out with acid and then filtered off at .50-.. The dyestut'f acid thus obtained is pasted with the requisite quantity of sodium carbonate for neutraliza- ..tion, and is then dried.

Thedyestuif dyes cotton and regenerated cellulose from aqueous solution in beautiful green shades of very good fastness properties.-

Example 10 5 parts by volume of aqueous sodium hydroxide solu- 7 tion of. 10% strength, 1.9 parts of Compound V, 1.9 parts of Compound VIII, 4.1 parts of Compound VII and 2 parts of Compound IX are dissolved in 400 parts of water and, at 10 and a pH of 4-6, 1.9 parts of chlorofurnaryl dichloride are added. The initial pH value is maintained by means of dilute aqueous sodium hydroxide solution. Upon completion of the resultant condensation, the dyestufr" is worked up as in the preceding examples. It dyes cotton and regenerated cellulose from aqueous solution in bluish green shades.

Example 1 formed green dyestufl? is precipitated with hydrochloric acid and then converted into the sodium salt in conventional manner. It is readily soluble in the dyebath, draws very well onto cotton and regenerated cellulose and dyes the fibers in beautiful green shades of outstanding light-fastness and Wet-fastriess.

Example 12 1.9 parts of Compound VI, 1.9 parts of 4-(4-aminobenzoyl)-amino-1,1-azobenzene-3,4-disulfonic acid, 4.5 parts of Compound VII, 0.6 part of 4-amino-1,1'-azo- 'cotton andregeneratedcellulose in green shades of good benzenel-sulfonic acid and parts by volume of aqueous sodium hydroxide solution of strength are dissolved in 350 parts of water. At a pH of 4-6, 10.5 parts by volume of a molar solution of fumaryl dichloride in carbon tetrachloride are added, and the pH maintained at its original value by means of dilute aqueous sodium hydroxide solution. Upon completion of the ensuing reaction, the mixture is warmed to distil off the carbon tetrachloride, after which the dyestufif is salted out and isolated. It dissolves with green coloration in water, 10 and dyes cotton'and regenerated cellulose in green shades of good fastness properties.

Example 13 Into 300 parts ofwater, there are stirred 0.6 part of lithium carbonate, 2.1 parts'of Compound VII, 2.9 parts of Compound V, 3.15 parts of Compound III and 1.4 parts of 4-amino-1,1-azobenzene-4-sulfonic acid. After the reaction mixture has been cooled to 0-5 and adjusted to a weakly acid reaction, 1.6 parts of fumaryl dichloride are added. Evolved HCl is neutralized with dilute aqueous sodium hydroxide solution. Upon completion of the condensation, aqueous sodium hydroxide solution of 30% strength is added until the reaction mixture has a strong alkaline reaction, parts of sodium sulfate are added, and the separated dyestuif suction-filtered ofl. It dissolves readily in water and in the dyebath with yellowish green coloration, and dyes cotton and regenerated cellulose yellowish green. The exchaustion capacity is excellent, and the dyeings are of very good light fastness and Wet-fastness.

Example .14

In 350 parts of Water, 0.9 part of lithium carbonate, 6.2 parts of Compound VII, 1.45 parts of Compound V and 1.5 parts of Compound III are dissolved. At 0-5 and a pH of 5-7, 1.6 parts of fumaryl dichloride are added I SOsH and the pH maintained constant with dilute aqueous sodium hydroxide solution. Upon completion of the ensuing reaction, 3.5 parts of sodium chloride and 20 parts by volume of aqueous sodium hydroxide solution of 29% strength are added, and the precipitated green dyestuif is filteredoif. From an aqueous solution, this dyestuif dyes 5Q fastness properties.

Example 15 Into 500 parts of water, there are stirred 5 parts (1.2 '5 molecular proportions) of Compound VII, i. e. of the compound of the formula N and 3.4 parts (0.8 molecular proportion) of the aminoazo dyestutf of the formula and 5.5 parts aqueous sodium hydroxide solution of 10% strength. At 0-5 1.6 parts of fumaryl dichloride are then added dropwise, the reactionbeing maintained weakly alkaline (pH 7-8.5) with the aid. of dilute aqueous sodium hydroxide solution. Upon completion of the resultant condensation, the reaction mixture is heated to and 6 parts of crystalline sodium acetate and 14.5 parts of aqueous copper sulfate solution of 20% strength are added. The mixture is maintained for 15 more minutes at 80, with stirring, and then the formed cupriferous dyestuff is precipitated from the solution with 36 parts of sodium chloride, and then'suction-filtered OE and dried.

The cupriferous dyestutidraws from aqueous solution onto cotton and regenerated cellulose in beautiful green shades of outstandinglight-fastness and 'wet-fastness.

Example 16 3.4 parts of Compound VII and 5.1 parts of the aminoazo dyestuff of Formula 7 are dissolved in 500 parts of water and 5.5 partsof aqueous sodium hydroxide solution of 10% strength. At 0-5, 1.6 parts of fumaryl dichloride are added dropwise, the pH of the reaction mixture being maintained at 7-8 with the aid of dilute aqueous sodium hydroxide solution. Upon completion of the ensuing condensation, the reaction mixture is heated to 80, and the dyestuif acid thrown down with hydrochloric acid and then suction-filtered oil.

The moist dyestuif is neutralized with sodium carbonate; to the resultant paste, 6 parts of crystalline sodium acetate and 24 parts of aqueous copper sulfate solution of 20% strength are added. After drying, there is obtained a cupriferous dyestuff which dyes cotton and regenerated cellulose from aqueous solution in yellowish green shades with outstanding fastness properties.

Example 17 5.9 parts of Compound VII and 5.9 parts of the eupriferous aminoazo dyestulf of the formula droxide solution. Upon completion of the condensation,

the carbon tetrachloride is distilled off, the dyestuff is saltedout at 80 with 80 parts of potassium chloride, after which the dyestutf is suction-filtered off cold and dried.

The dyestuff dissolves readily in Water and draws from the dyebath onto cotton and regenerated cellulose in beautiful green shades with very good light-fasteness and Wet-fastness properties.

Example 18 9.8 parts (1.2 molecular proportions) of Compound VII, i. e. of the compound of the formula wise in the course of a half hour.

swarm 7 l1 and 4.6- parts (0.8 molecular proportion) of the compound of the formula (4" -a'm'ino-l,l"azobenzene-4-sulfonic acid) are dissolved in 600 parts of Water and 5 parts of aqueous sodium hydroxide solution of strength. At 0-5 and at pH 7-8.5, 3.5 parts of fumaryl dichloride are added drop- Correction of the acidity is effected with dilute aqueous sodium hydroxide "solution. When the ftimaryl dichloride has becn'entirely consumed, the solution warmed to 80, and the dyestufi acid precipitated with 60 parts of 30% hydrochloric acid and filtered oil. The dyestuff acid isthen neutralized with sodium carbonate and'dried.

, The thus-obtained dyestuff is a dark green powder which dyes cotton and regenerated cellulose from aqueous Example 1 1 part of the dyestuff prepared according to Example 3, first paragraph, is ground together with /2 part of sodium metaphosphate and /2 part of urea and then dissolved in 200 parts of boiling water. The solution is poured into 3000 parts of water, 40 parts of anhydrous sodium sulfate are added, and at 30 100 parts of prewetted cotton material introduced. The solution is warmed to80 and maintained at 80-'90 for 30 minutes, thereupon boiled for minutes and then cooled to 60. The material is then rinsed and dried. A deep green dyeing is obtained.

Example By replacing the starting anthraquinone compounds of Example 11 by a mixture of 5.45 parts of Compound VII, 2.35 parts of Compound XII and 1.3 parts of Compound V, and otherwise proceeding in the same manner as described in such example, a similar green dyestuti is obtained.

Example 21 The process according to Example 11 is repeated except that the 2.2 parts of Compound VI are replaced by 2.6'parts of Compound XIIi. A dyestuff dyeing cotton and fibers made from regenerated cellulose in beautiful green shades of very good fastness to light and to wet treatments is obtained.

1. A green substantive dye obtained by condensing, in molecular proportions which difier from each other by at least 10%, a 1-aminoanthraquinone-2-sulfonic acid wherein R stands for a member selected from the group consisting of monoand binuclear radicals of the benzene series, v stands for a member selected from the group consisting of hydrogen, lower alkyl, lower alkoxy and 8031?, w standsfo'r a member selected from the group cons1sting of hydrogen, lower alkyl and lower alkoxy, x

" Having thus disclosed the invention, what isclaimed stands for a member selected from the group consisting of hydrogen, chlorine, bromine and SOsH, and y stands for a member selected from the group consisting of hydrogen and chlorine, with at least one I-aminoanthraquinone-Z-sulfonic acid different from the first one but corresponding to the aforesaid formula, by treating them with such a quantity of a dicarboxylic acid halide corresponding to the formula wherein 1 stands for a member selected from the group consisting of chlorine and bromine, and A stands for a member selected from the group consisting of hydrogen, methyl, chlorine and bromine, that there are for each molecule of the dicarboxylic acid halide two molecules of 1nminoanthraquinone-2-sulfonic acid.

2. The green substantive dye obtained by condensing 1.45 molecular proportions of the 1-aminoanthraquinone- Z-Suifonic acid corresponding to the formula (I? lTTHz C@SO3H 0 NH Mn and 0.55 molecular proportion of the l-aminoanthraquinone-Z-sulfonic acid corresponding to the formula (M) NH:

with 1 molecular proportion of fumaric acid dichloride.

3. The green substantive dye obtained by condensing 1.4 molecular proportions of the l-aminoanthraquinone- 2-sulfonic acid corresponding to the formula (i b THONH: and 0.6 molecular proportion of the l-aminoanthraquinone-2-sulfonic acid corresponding to the formula NHt NHa . SOaH with. 1 molecular proportion of fumaric acid dichloride. 4. The green substantive dye obtained by condensing 0.25 molecular proportion of the l-aminoanthraquinone- 2-sulfonic acid corresponding to the formula O NH:

SOaH

HOES V 0.25 molecular proportion of the I-aminoanthraquinone- 'Z-sulfonic acid corresponding to the formula i NHONH:

and 1.5 molecular proportions of the LaminQanthraquinone-Z-sulfonic acid corresponding to the formula SOsH ( i NEG-NH:

with 1 molecular proportion of fumaric acid dichloride.

5. The green substantive dye obtained by condensing 1.0 molecular proportion of the l-aminoanthraquinone- Z-sulfonic acid corresponding to the formula NH: II

(N) NHONH,

0.5 molecular proportion of the l-aminoanthraquinone-Z- sulfonic acid corresponding to the formula (I? NH:

I o NHQNH:

0.25 molecular proportion of the l-aminoanthraquinone- 2-sulfonic acid corresponding to the formula i) NEG-NH,

HOaS

14 and 0.25 molecular proportion of the l-aminoanthraquinone-2-sulfonic acid corresponding to the formula NHa with 1 molecular proportion of fumaric acid dichloride.

6. The green substantive dye obtained by condensing 0.22 molecular proportion of the l-arninoanthraquinone- 2-sulfonic acid corresponding to the formula 01 S 0 all 0.45 molecular proportion of the l-aminoanthraquinone- 2-sulfonic acid corresponding to the formula --s on;

BOSS

( NHONE and 1.33 molecular proportions of the l-aminoanthraqninone-2-sulfonic acid corresponding to the formuh References Cited in the file of this patent UNITED STATES PATENTS Honold et al. Jan. 14, 1941 Peter et a1. Dec. 30, 1952 

1. A GREEN SUBSTANTIVE DYE OBTAINED BY CONDENSING IN MOLECULAR PROPORTIONS WHICH DIFFER FROM EACH OTHER BY AT LEAST 10%, A 1-AMINOANTHRAQUINONE-2-SULFONIC ACID CORRESPONDING TO THE FORMULA WHEREIN R STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF MONO-ANDD BINUCLEAR RADICALS OF THE BENZENE SERIES, V STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL, LOWER ALKOXY AND SO3H, W STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, LOWER ALKYL AND LOWER ALKOXY, X STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, CHLORINE, BROMINE AND SO3H, AND Y STANDS FOR A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGEN AND CHLORINE, WITH AT LEAST ONE 1-AMINOANTHARAQUINONE-2-SULFONIC ACID DIFFERENT FROM THE FIRST ONE BUT CORRESPONDING TO THE AFORESAID FORMULA, BY TREATING THEM WITH SUCH A QUANTITY OF A DICARBOXYLIC ACID HALIDE CORRESPONDING TO THE FORMULA 